JP2002292273A - Plasma reactor and plasma reaction method - Google Patents
Plasma reactor and plasma reaction methodInfo
- Publication number
- JP2002292273A JP2002292273A JP2001103738A JP2001103738A JP2002292273A JP 2002292273 A JP2002292273 A JP 2002292273A JP 2001103738 A JP2001103738 A JP 2001103738A JP 2001103738 A JP2001103738 A JP 2001103738A JP 2002292273 A JP2002292273 A JP 2002292273A
- Authority
- JP
- Japan
- Prior art keywords
- plasma
- reactor
- gas
- discharge
- reaction method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00054—Controlling or regulating the heat exchange system
- B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
- B01J2219/00058—Temperature measurement
- B01J2219/00063—Temperature measurement of the reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
- B01J2219/00081—Tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
- B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
- B01J2219/0824—Details relating to the shape of the electrodes
- B01J2219/0835—Details relating to the shape of the electrodes substantially flat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
- B01J2219/0845—Details relating to the type of discharge
- B01J2219/0847—Glow discharge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0875—Gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はプラズマ反応装置及
びプラズマ反応方法に関し、、例えば、工業工程などか
ら排出されるＶＯＣ（揮発性有機化合物）を含有する気
体を分解するプラズマ反応装置または方法に係り、連続
した分解反応を行う場合でも安定して高分解率が得られ
る排ガス浄化装置等に適するプラズマ反応装置または方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma reaction apparatus and a plasma reaction method, and more particularly to a plasma reaction apparatus and method for decomposing a gas containing VOC (volatile organic compound) discharged from an industrial process or the like. relates to stable plasma reactor or method suitable for high degradation rate exhaust gas purifying apparatus and the like obtained even when performing continuous decomposition reaction.
【０００２】[0002]
【従来の技術】揮発性有機化合物（Ｖｏｌａｔｉｌｅ
Ｏｒｇａｎｉｃ Ｃｏｍｐｏｕｎｄｓ（ＶＯＣ）；以下
ＶＯＣと記す。）を含有するガスを分解処理する方法と
して非平衡プラズマ法がある。非平衡プラズマ法は、常
温常圧で広い濃度範囲のＶＯＣが短時間で分解でき、装
置構成も簡単であるなどの利点が明らかとなっている。
そして、常圧下で放電を発生させる方法は数多く開発さ
れており、その方法は、無声放電、沿面放電、パルスコ
ロナ放電、パックトベッド放電に大別できる。2. Description of the Related Art Volatile organic compounds (Volatile)
Organic Compounds (VOC); hereinafter referred to as VOC. Non-equilibrium plasma method is known as a method for decomposing a gas containing ()). The advantages of the non-equilibrium plasma method, such as that VOCs in a wide concentration range can be decomposed in a short time at normal temperature and normal pressure, and the apparatus configuration is simple, have been clarified.
A number of methods for generating a discharge under normal pressure have been developed, and the methods can be broadly classified into silent discharge, creeping discharge, pulse corona discharge, and packed bed discharge.
【０００３】無声放電は電極間距離が数ｍｍ程度と短
く、大容量のガスで安定した放電を得るためには反応器
を数多く用意する必要がある。また沿面放電はセラミッ
クスなどの無機物表面と内部に電極を形成し交流電圧を
印加するとセラミックス表面に放電が発生するもので極
めて部分的な放電状態となる。これらの問題点を解決す
べき方法として無機誘電体を充填したパックトベッド式
がある。パックトベッド式プラズマ装置はリアクター内
に無機誘電体として比誘電率（ε）１０００〜１０００
０のＢａＴｉＯ3（チタン酸バリウム）やチタン酸スト
ロンチウムを充填して、グロー放電を発生させることを
特徴とするものである。In the silent discharge, the distance between the electrodes is as short as about several mm, and it is necessary to prepare many reactors in order to obtain a stable discharge with a large volume of gas. The creeping discharge is extremely partial discharge state in which discharge is generated in the ceramic surface is applied an inorganic surface and an internal forming electrodes with alternating voltage, such as ceramics. As a method for solving these problems, there is a packed bed type filled with an inorganic dielectric. The packed bed type plasma apparatus has a relative dielectric constant (ε) of 1000 to 1000 as an inorganic dielectric in a reactor.
BaTiO 3 0 was filled with (barium titanate) or strontium titanate, is characterized in that for generating a glow discharge.
【０００４】[0004]
【発明が解決しようとする課題】上記したパックトベッ
ド式プラズマ装置によるＶＯＣ分解処理は、各種ＶＯＣ
に対して有効である。しかしながら、従来の大気圧プラ
ズマ反応装置では、時間の経過とともにリアクター内の
温度が上昇し、それに伴い電流値の減少が起こるため、
安定した放電を維持することは困難であり、長時間の連
続使用は不可能であった。また、リアクター内の温度が
高くなると、電流電圧特性が変化するだけでなく、分解
率の低下、中間副生成物の生成など分解反応にも悪影響
を及ぼす等の問題点を有している。すなわち、リアクタ
ー形状・容量、反応条件によっても温度特性は異なる
が、連続して１〜２時間程度使用した場合、リアクター
内の温度は１００℃前後にまで達することもあり、その
結果、分解率は大きく低下する。The VOC decomposition process using the packed bed type plasma apparatus described above involves various VOCs.
Is effective for However, in a conventional atmospheric pressure plasma reactor, the temperature inside the reactor increases with time, and the current value decreases accordingly,
It was difficult to maintain stable discharge, and continuous use for a long time was impossible. Further, the temperature in the reactor is high, not only the current-voltage characteristic changes, decreased degradation rates, is also a problem, such as adverse effects on product decomposition reaction of the intermediate-products. That is, the temperature characteristics vary depending on the reactor shape / capacity and reaction conditions, but when used continuously for about 1 to 2 hours, the temperature inside the reactor may reach up to around 100 ° C., and as a result, the decomposition rate It greatly decreases.
【０００５】このようなことから、従来の装置では連続
して安定な反応を行うことは難しく、仮に電圧をコント
ロール（増加）することにより一時的に高い分解率を達
成しても、長時間の使用には対応できず、この方法には
限界がある。また、温度上昇を低く抑える方法として誘
電率の低い（ε＜１００）の無機誘電体を使用する方法
があるが、誘電率の低い誘電体を使用した場合、分解率
が低下することが懸念される。[0005] For this reason, it is difficult to perform a stable reaction continuously with the conventional apparatus. Even if a high decomposition rate is temporarily achieved by controlling (increasing) the voltage, a long time is required. It cannot be used and this method has its limitations. Further, as a method for suppressing the temperature rise, there is a method using an inorganic dielectric having a low dielectric constant (ε <100). However, when a dielectric having a low dielectric constant is used, there is a concern that the decomposition rate may be reduced. You.
【０００６】一方、ＶＯＣの種類によってはリアクター
内温度が２５℃以下の場合、凝縮が起こり、反応が十分
に進まないこともある。従ってリアクター内の温度が所
定値よりも低い場合、もしくは冷却により温度が下がっ
てしまった場合は、温度を上昇させることが必要となっ
てくる。また、ＶＯＣの種類、混合状態等によっても最
適反応温度は異なることから、リアクター内の温度をコ
ントロールすることは重要な問題である。On the other hand, depending on the type of VOC, when the temperature inside the reactor is 25 ° C. or lower, condensation occurs and the reaction may not proceed sufficiently. Therefore, when the temperature in the reactor is lower than a predetermined value, or when the temperature is lowered by cooling, it is necessary to increase the temperature. Further, since the optimum reaction temperature varies depending on the type of VOC, the mixing state, and the like, it is important to control the temperature in the reactor.
【０００７】そこで、本発明は、上記課題を解決し、気
体をプラズマ化し、このプラズマのもつエネルギーを利
用して連続処理する場合において、安定した反応によっ
て処理を行うことが可能なプラズマ反応装置及びプラズ
マ反応方法を提供することを目的とするものである。Accordingly, the present invention has been made to solve the above-mentioned problems, and to provide a plasma reactor and a plasma reaction apparatus capable of performing a stable reaction in the case of converting a gas into plasma and performing continuous processing using the energy of the plasma. It is an object of the present invention to provide a plasma reaction method.
【０００８】[0008]
【課題を解決するための手段】本発明は、上記課題を達
成するため、つぎの（１）〜（２０）のように構成した
プラズマ反応装置及びプラズマ反応方法を提供するもの
である。 （１）リアクター内に高電位側と低電位側の電極が配さ
れ、該電極間に気体が流れることが可能な構造を有する
無機誘電体が充填された構成を備え、該電極間に放電を
発生させて該電極間に存在する気体をプラズマ化して処
理するプラズマ反応装置であって、前記リアクター内の
温度を調節する温度調節手段を有することを特徴とする
プラズマ反応装置。 （２）前記温度調節手段が、前記電極に媒体を流通させ
るための配管を配することによって構成されていること
を特徴とする上記（１）に記載のプラズマ反応装置。 （３）前記低電位側の電極を接地状態とし、該接地電極
に前記配管が配されていることを特徴とする上記（２）
に記載のプラズマ反応装置。 （４）前記電極間に存在する気体を、常圧下においてプ
ラズマ化することを特徴とする上記（１）〜（３）のい
ずれかに記載のプラズマ反応装置。 （５）前記放電が、グロー放電であることを特徴とする
上記（１）〜（４）のいずれかに記載のプラズマ反応装
置。 （６）前記放電により、前記気体中に存在する揮発性有
機化合物を分解するように構成されていることを特徴と
する上記（１）〜（５）のいずれかに記載のプラズマ反
応装置。 （７）前記無機誘電体が、気体が流れることが可能な隙
間を有し、かつ該無機誘電体間の隙間で放電が発生する
構造を有することを特徴とする上記（１）〜（６）のい
ずれかに記載のプラズマ反応装置。 （８）前記無機誘電体が、強誘電体であることを特徴と
する上記（１）〜（７）のいずれかに記載のプラズマ反
応装置。 （９）前記無機誘電体が、チタン酸バリウム、チタン酸
ストロンチウムから選択される少なくとも一つからなる
ことを特徴とする上記（１）〜（８）のいずれかに記載
のプラズマ反応装置。 （１０）前記無機誘電体が、粒状体であることを特徴と
する上記（１）〜（９）のいずれかに記載のプラズマ反
応装置。 （１１）リアクター内に高電位側と低電位側の電極間に
気体が流れることが可能な構造を有する無機誘電体を充
填し、該電極間に放電を発生させて該電極間に存在する
気体をプラズマ化して処理するプラズマ反応方法であっ
て、前記リアクター内を温度調節しながら、前記気体を
プラズマ化することを特徴とするプラズマ反応方法。 （１２）前記リアクター内の温度調節が、前記電極に配
された配管を流通する媒体を介して行われることを特徴
とする上記（１１）に記載のプラズマ反応方法。 （１３）前記低電位側の電極を接地状態とし、該接地電
極に前記配管が配されていることを特徴とする上記（１
２）に記載のプラズマ反応方法。 （１４）前記電極間に存在する気体を、常圧下において
プラズマ化することを特徴とする上記（１１）〜（１
３）のいずれかに記載のプラズマ反応方法。 （１５）前記放電が、グロー放電であることを特徴とす
る上記（１１）〜（１４）のいずれかに記載のプラズマ
反応方法。 （１６）前記放電により、前記気体中に存在する揮発性
有機化合物を分解することを特徴とする上記（１１）〜
（１５）のいずれかに記載のプラズマ反応方法。 （１７）前記無機誘電体が、気体が流れることが可能な
隙間を有し、かつ該無機誘電体間の隙間で放電が発生す
る構造を有することを特徴とする上記（１１）〜（１
６）のいずれかに記載のプラズマ反応方法。 （１８）前記無機誘電体が、強誘電体であることを特徴
とする上記（１１）〜（１７）のいずれかに記載のプラ
ズマ反応方法。 （１９）前記無機誘電体が、チタン酸バリウム、チタン
酸ストロンチウムから選択される少なくとも一つからな
ることを特徴とする上記（１１）〜（１８）のいずれか
に記載のプラズマ反応方法。 （２０）前記無機誘電体が、粒状体であることを特徴と
する上記（１１）〜（１９）のいずれかに記載のプラズ
マ反応方法。SUMMARY OF THE INVENTION The present invention provides a plasma reaction apparatus and a plasma reaction method configured as described in the following (1) to (20) in order to achieve the above object. (1) into the reactor is the high potential side and the low potential side of the electrode is arranged, a configuration in which the inorganic dielectric-filled with capable gas flow structure between the electrodes, the discharge between the electrodes by generating a plasma reactor for processing a gas existing between the electrodes and plasma, the plasma reactor characterized by having a temperature adjusting means for adjusting the temperature within said reactor. (2) the temperature adjusting means, a plasma reactor according to the above (1), characterized in that it is constituted by arranging the piping for circulating the medium to the electrode. (3) The above-mentioned (2), wherein the electrode on the low potential side is grounded, and the pipe is disposed on the ground electrode.
3. The plasma reactor according to claim 1. (4) the gas present between the electrodes, the plasma reactor of any of the above, characterized in that plasma under normal pressure (1) to (3). (5) The plasma reactor according to any one of (1) to (4), wherein the discharge is a glow discharge. (6) The plasma reactor according to any one of (1) to (5) above, wherein the discharge is configured to decompose a volatile organic compound present in the gas. (7) The above (1) to (6), wherein the inorganic dielectric has a gap through which gas can flow, and has a structure in which a discharge occurs in the gap between the inorganic dielectrics. The plasma reactor according to any one of the above. (8) The plasma reactor according to any one of (1) to (7), wherein the inorganic dielectric is a ferroelectric. (9) the inorganic dielectric, the plasma reactor according to any one of the above (1) to (8), characterized in that it consists of at least one selected barium titanate, strontium titanate. (10) The plasma reactor according to any one of the above (1) to (9), wherein the inorganic dielectric is a granular material. (11) The reactor is filled with an inorganic dielectric having a structure that allows gas to flow between the high-potential side electrode and the low-potential side electrode, and a discharge is generated between the electrodes to form a gas existing between the electrodes. A plasma reaction method, wherein the gas is converted into plasma while controlling the temperature inside the reactor. (12) The plasma reaction method according to the above (11), wherein the temperature inside the reactor is adjusted via a medium flowing through a pipe arranged on the electrode. (13) wherein the low-potential electrode and the ground state, wherein the pipe in the ground electrode is disposed above (1
The plasma reaction method according to 2). (14) The above (11) to (1), wherein the gas existing between the electrodes is converted into plasma under normal pressure.
The plasma reaction method according to any one of 3). (15) The plasma reaction method according to any one of (11) to (14), wherein the discharge is a glow discharge. (16) The above (11) to (11), wherein the discharge decomposes volatile organic compounds present in the gas.
The plasma reaction method according to any one of (15). (17) The above-mentioned (11) to (1), wherein the inorganic dielectric has a gap through which gas can flow, and has a structure in which a discharge occurs in the gap between the inorganic dielectrics.
The plasma reaction method according to any one of 6). (18) The plasma reaction method according to any one of (11) to (17), wherein the inorganic dielectric is a ferroelectric. (19) The plasma reaction method according to any one of (11) to (18), wherein the inorganic dielectric is made of at least one selected from barium titanate and strontium titanate. (20) The plasma reaction method according to any one of the above (11) to (19), wherein the inorganic dielectric is a granular material.
【０００９】[0009]
【発明の実施の形態】本発明の実施の形態においては、
上記構成を適用して、リアクター内を冷却及び加熱する
ことができる温度調節手段を構成することによって、リ
アクター内の温度を所定範囲内に保つようコントロール
し、それにより安定した放電を可能とすることで、高い
分解率を維持することが可能となる。例えば、ＶＯＣの
プラズマ分解処理を連続して行う場合、放電により生ず
るリアクター内の温度変化を、冷却機能及び加熱機能を
有する温度調節器を用いて温度コントロールすることに
より、長時間、高分解率で安定した分解反応を行うこと
が可能となる。DESCRIPTION OF THE PREFERRED EMBODIMENTS In an embodiment of the present invention,
By applying the above-described configuration and configuring a temperature adjusting means capable of cooling and heating the inside of the reactor, the temperature in the reactor is controlled to be kept within a predetermined range, thereby enabling a stable discharge. Thus, a high decomposition rate can be maintained. For example, when performing the plasma decomposition treatment of VOCs continuously, the temperature change in the reactor caused by the discharge is controlled by using a temperature controller having a cooling function and a heating function, so that a long time and high decomposition rate can be obtained. A stable decomposition reaction can be performed.
【００１０】具体的な方法としては、電極板内に配され
た配管内に冷水、温水を循環させることにより冷却・加
温することができる手段、もしくは、電極板内に冷却及
び加熱することができる温度調節器を構成することによ
り、リアクター内の温度をコントロールすることが可能
となる。その際、温冷水を使用する場合、冷却水、温水
を循環させる配管の断面はどのような形状、例えば円
形、多角形など、いずれの形状でも差し支えない。反応
条件、リアクター内の温度状態により水温・水量を調整
するようにすることができる。また、配管もしくは温度
調節器は、リアクター全体を均一に温度調節できるよう
に、電極板内に配置することができる。また、リアクタ
ー構造は、同軸円筒タイプ、平行平板タイプのいずれで
もよく、層数もガス処理量に応じて任意に変更できるも
のとする。[0010] As a specific method, the cold water in the piping disposed on the electrode within the plate, means can be cooled and heated by circulation of hot water, or, to be cooled and heated in the electrode in the plate By configuring a temperature controller that can be used, it is possible to control the temperature inside the reactor. In this case, when hot and cold water is used, the cross section of the pipe for circulating the cooling water and the hot water may have any shape, for example, a circular shape or a polygonal shape. The temperature and amount of water can be adjusted depending on the reaction conditions and the temperature inside the reactor. Further, the pipe or the temperature controller can be arranged in the electrode plate so that the temperature of the entire reactor can be uniformly adjusted. Further, the reactor structure may be any of a coaxial cylindrical type and a parallel plate type, and the number of layers may be arbitrarily changed according to a gas processing amount.
【００１１】冷却機能、加熱機能を接地電極に設けるこ
とにより、効率良く温度コントロールすることが可能と
なる。電流電圧特性は、リアクター温度が６０℃前後に
なると、電流は初期値と比較して２〜３割程度低下す
る。また、ＶＯＣの種類によっては室温（２５℃）以下
では凝縮が起こり、反応が十分に進まないことがある。
従って、高分解率を維持して反応を行うためには、２５
〜６０℃望ましくは３０〜５０℃に保つことが必要であ
る。またリアクター内温度を一定に保つことにより、分
解率を維持することが可能である。また、リアクター内
の温度は、常にモニタリングされており、反応に最適な
温度範囲内で反応が行えるよう制御されるように構成す
ることができる。By providing a cooling function and a heating function on the ground electrode, it is possible to control the temperature efficiently. Current-voltage characteristic, the reactor temperature is around 60 ° C., the current decreases by about 20-30% compared to the initial value. Also, depending on the type of VOC condensation occurs at room temperature (25 ° C.) or less, sometimes the reaction does not proceed sufficiently.
Therefore, in order to carry out the reaction while maintaining a high decomposition rate, 25
To 60 ° C, preferably 30 to 50 ° C. Further, by maintaining the reactor in a constant temperature, it is possible to maintain the decomposition rate. In addition, the temperature inside the reactor is constantly monitored, and the reactor can be configured to be controlled so that the reaction can be performed within the optimum temperature range.
【００１２】以下に、本発明の実施の形態におけるガス
分解装置の一例について、さらに詳細に説明する。図１
は、本実施の形態に係るガス分解装置の構成図である。
また、図２は、本実施の形態で使用するリアクター１を
気体の流れに平行な面で切断した断面図であり、図３
は、本実施の形態で使用するリアクター１を気体の流れ
に垂直な断面で切断した断面図である。また、図４は、
本実施の形態に係るガス分解装置における接地電極板の
断面図であり、冷水・温水を循環させるための配管１６
を備えている。Hereinafter, an example of the gas decomposition apparatus according to the embodiment of the present invention will be described in more detail. Figure 1
1 is a configuration diagram of a gas decomposition apparatus according to the present embodiment.
FIG. 2 is a cross-sectional view of the reactor 1 used in the present embodiment cut along a plane parallel to the gas flow.
Is a cross-sectional view of the reactor 1 to be used by cutting in a cross section perpendicular to the flow of gas in this embodiment. Also, FIG.
It is sectional drawing of the ground electrode plate in the gas decomposition apparatus which concerns on this Embodiment, The piping 16 for circulating cold water and hot water is shown.
It has.
【００１３】図２および図３に示すように、リアクター
１は、５枚の電極を有し、それらが高電位側と低電位側
に接続されている。ここでは、高電位側の第１電極５、
第３電極７及び第５電極９に対して、低電位側の第２電
極６及び第４電極８が配された電極構成が採られてい
る。第１電極５、第３電極７及び第５電極９は、交流電
源２に接続されており、電源により電極に交流電圧をか
けることができるようになっている。また、第２電極６
及び第４電極８は、電気的に接地状態である。[0013] As shown in FIGS. 2 and 3, the reactor 1 has a five electrodes, they are connected to the high potential side and the low potential side. Here, the first electrode 5 on the high potential side,
An electrode configuration in which the second electrode 6 and the fourth electrode 8 on the low potential side are arranged with respect to the third electrode 7 and the fifth electrode 9 is employed. The first electrode 5, the third electrode 7, and the fifth electrode 9 are connected to the AC power supply 2, so that an AC voltage can be applied to the electrodes by the power supply. The second electrode 6
And the fourth electrode 8 is electrically grounded.
【００１４】これらの電極数は、装置規模により任意に
決定することができ、処理流量が大きい時には電極枚数
を増加させることで、処理効率を下げることなく装置規
模を上げることができる。また、それぞれの電極の間に
は無機誘電体１０が充填されている。無機誘電体として
は、比誘電率１０００〜１００００のチタン酸バリウム
やチタン酸ストロンチウムのような強誘電体が望まし
い。また、無機誘電体の形状は、図２、３に示すよう
に、無機誘電体の空間を通ってガスが透過でき、かつ誘
電体間の隙間で放電が発生する構造を有する粒状、望ま
しくは球状のものが良い。[0014] The number of these electrodes can be arbitrarily determined by the apparatus scale, by increasing the number of electrodes when the processing flow is large, it is possible to increase the apparatus size without decreasing the processing efficiency. The space between the electrodes is filled with an inorganic dielectric 10. As the inorganic dielectric, ferroelectric such as barium titanate or strontium titanate dielectric constant 1000-10000 is preferable. Further, as shown in FIGS. 2 and 3, the shape of the inorganic dielectric is a granular shape, preferably a spherical shape, having a structure in which gas can pass through the space of the inorganic dielectric and discharge occurs in the gap between the dielectrics. Is good.
【００１５】ＶＯＣガスは、リアクター入口１１より入
り、拡散空間１２に入り込む。ＶＯＣガスに特に制限は
ない。拡散空間１２と無機誘電体１０の充填されたプラ
ズマスペースとはテフロン（登録商標）の様な絶縁体材
料でなるメッシュなど気体が通過できる構造の絶縁体仕
切り１３で仕切られており、無機誘電体１０は拡散空間
１２には入り込まない構造となっている。[0015] VOC gas enters from the reactor inlet 11, enters the diffusion space 12. There is no particular limitation on the VOC gas. The diffusion space 12 and the plasma space filled with the inorganic dielectric 10 are separated by an insulator partition 13 having a structure through which gas can pass, such as a mesh made of an insulating material such as Teflon (registered trademark). 10 has a structure that does not enter the diffusion space 12.
【００１６】拡散空間に入った気体は、絶縁体仕切り１
３を通過して無機誘電体の充填されたプラズマスペース
に入る。ここで電極１及び電極３及び電極５に交流電圧
をかけることでグロー放電が起こり、プラズマが発生す
る。この際、ＶＯＣガス中のＶＯＣ成分がプラズマのエ
ネルギーにより分解処理される。The gas that has entered the diffusion space is the insulator partition 1
3 through the fall filled plasma space inorganic dielectric. Here, glow discharge occurs by applying an AC voltage to the electrode 1, the electrode 3, and the electrode 5, and plasma is generated. At this time, the VOC component in the VOC gas is decomposed by the energy of the plasma.
【００１７】連続して分解処理を行った場合、放電の影
響により、リアクター内に温度変化が生ずるが、配管１
６に温冷水器からの温水、冷水を循環させることによ
り、リアクター内の温度を一定に保つ。配管１６は図４
のように断面は円形で、蛇行した構造をとっており、上
記したように接地電極６、７に配されている。接地電極
板の上部から注入された温・冷水は配管内を流通し、下
部から排出され、さらに温冷水器へ戻って温度調整され
た後、配管内を循環することにより、リアクターを温度
コントロールするものである。リアクター内の温度は、
電極板に取り付けられた温度センサーにより、常時モニ
タリングされている。装置内で分解処理されたＶＯＣガ
スは気体出口１４より排出される。When the decomposition treatment is performed continuously, a temperature change occurs in the reactor due to the influence of electric discharge.
Hot water from the hot water cooler to 6, by circulating cold water, keeping the temperature in the reactor constant. Pipe 16 Figure 4
Section is circular, has taken meandering structure are arranged in the ground electrode 6, 7 as described above as. The hot / cold water injected from the upper part of the ground electrode plate flows through the pipe, is discharged from the lower part, returns to the hot / cold water heater, is temperature-controlled, and circulates in the pipe to control the temperature of the reactor. it is intended. The temperature inside the reactor is
The temperature sensor attached to the electrode plate is constantly monitored. Decomposition treated VOC gas in the apparatus is discharged from the gas outlet 14.
【００１８】[0018]
【実施例】以下に、本発明の実施例について説明する。
なお、本実施例で用いた実験装置を含む実験条件の内容
は、つぎのとおりである。なお、分解率に関しては、リ
アクターの入口・出口にてガスをテドラーバッグに採取
し、ＧＣＭＳ（ガスクロマトグラフ質量分析計）にて分
析し、ＶＯＣガスの出口濃度／入口濃度より算出した。 ・放電分解装置：粒径３ｍｍのチタン酸バリウム（Ｂａ
ＴｉＯ3；ε＝７０００）ペレットを充填したパックト
ベッド式放電装置。 ・リアクター寸法：電極板 ６００ × １２０ｍｍ、
電極間距離 １５ｍｍ×４層。 ・サンプルガス：１００ｐｐｍメタノールガス ・冷却水・温水：冷却水 水温 １５℃、流量 ２５〜
３０ｍｌ／ｍｉｎ、温 水 水温 ４０℃、流量 ４０
〜５０ｍｌ／ｍｉｎ。Embodiments of the present invention will be described below.
The contents of the experimental conditions including the experimental apparatus used in this example are as follows. In addition, about the decomposition rate, gas was sampled in a Tedlar bag at the inlet and outlet of the reactor, analyzed by GCMS (gas chromatograph mass spectrometer), and calculated from the VOC gas outlet concentration / inlet concentration.・ Electrolytic decomposition device: barium titanate (Ba having a particle diameter of 3 mm)
(TiO 3 ; ε = 7000) A packed bed discharge device filled with pellets.・ Reactor dimensions: Electrode plate 600 × 120mm,
Electrode distance 15 mm × 4 layers.・ Sample gas: 100 ppm methanol gas ・ Cooling water ・ Hot water: Cooling water Water temperature 15 ° C., flow rate 25-
30ml / min, hot water, water temperature 40 ° C, flow rate 40
５０50 ml / min.
【００１９】［実施例１］実施例１においては、リアク
ター初期温度２５℃の状態に２．５ｋＶの電圧を印加
し、リアクター内温度が４０℃に達した時点からメタノ
ールガスを８０ｌ／ｍｉｎで流通した。さらに冷却水、
温水を使用し、リアクター内温度を４０±５℃保つよう
コントロールした。この時の電流値の経時変化を図５に
示す。図５より、リアクター内で安定した放電が発生し
ていることが確認できる。Example 1 In Example 1, a voltage of 2.5 kV was applied to the reactor at an initial temperature of 25 ° C., and methanol gas was flowed at 80 l / min when the temperature in the reactor reached 40 ° C. did. Further cooling water,
The temperature in the reactor was controlled to be maintained at 40 ± 5 ° C. using hot water. FIG. 5 shows a temporal change of the current value at this time. From FIG. 5, it can be confirmed that stable discharge has occurred in the reactor.
【００２０】［実施例２］実施例２においては、リアク
ター温度が４０℃に達した時点でメタノールガスを８０
ｌ／ｍｉｎで流通させ２．５ｋＶ、２３０ｍＡの処理条
件で連続して分解反応を行った。分解反応開始直後の分
解率は８９％、６０分経過後の分解率は８８％、１２０
分経過後の分解率は８９％で分解率の経時変化は見られ
なかった。Example 2 In Example 2, when the reactor temperature reached 40.degree.
2.5kV was circulated in l / min, it was carried out decomposition reaction continuously in process conditions 230 mA. Decomposition rate immediately after the start of the decomposition reaction is 89%, the decomposition rate after 60 minutes is 88%, 120
Degradation rate after minute elapsed time course of degradation rate of 89% was observed.
【００２１】（比較例１）比較例１においては、リアク
ターにメタノールガスを８０ｌ／ｍｉｎで流通させ、
２．５ｋＶの電圧を印加し、連続運転を行った。この
時、冷却水・温水による温度コントロールは行わない。
リアクター内の温度変化、電流値の経時変化を測定し
た。その結果を図６に示す。３０分間の連続運転でリア
クター温度は２７℃から７１℃まで上昇し、電流値は２
３０ｍＡから１８７ｍＡまで低下した。また９０分経過
後、リアクター温度は９７℃まで上昇し、電流値１２１
ｍＡまで低下した。[0021] (Comparative Example 1) Comparative Example 1, was passed through methanol gas 80l / min to the reactor,
A voltage of 2.5 kV was applied to perform a continuous operation. At this time, temperature control with cooling water and hot water is not performed.
The temperature change in the reactor was measured with time change in the current value. The result is shown in FIG. After 30 minutes of continuous operation, the reactor temperature increased from 27 ° C to 71 ° C, and the current value was 2
It dropped from 30 mA to 187 mA. After 90 minutes, the reactor temperature rose to 97 ° C.
It was lowered to mA.
【００２２】（比較例２）比較例２においては、上記比
較例１において分解開始後、３０分後及び９０分後の分
解率を測定した。分解開始直後の分解率は８９％であっ
た。３０分経過後は７８％、９０分経過後は６４％とリ
アクター温度の上昇とともに分解率の低下が見られた。Comparative Example 2 In Comparative Example 2, the decomposition rates of Comparative Example 1 were measured 30 minutes and 90 minutes after the start of decomposition. The decomposition rate immediately after the start of decomposition was 89%. After 30 minutes, the decomposition rate was 78%, and after 90 minutes, 64%.
【００２３】（比較例３）比較例３においては、リアク
ター温度２０℃に保ちメタノールガスを８０ｌ／ｍｉｎ
で流通しながら、２．５ｋＶ、２２０ｍＡで分解反応を
行った。分解率を測定したところ６０％であった。Comparative Example 3 In Comparative Example 3, the reactor temperature was kept at 20 ° C., and methanol gas was supplied at 80 l / min.
, And a decomposition reaction was performed at 2.5 kV and 220 mA. The decomposition rate was measured to be 60%.
【００２４】[0024]
【発明の効果】以上に説明したように、本発明によれ
ば、気体をプラズマ化し、このプラズマのもつエネルギ
ーを利用して連続処理する場合において、安定した反応
によって処理を行うことが可能なプラズマ反応装置及び
プラズマ反応方法を実現することができる。As described above, according to the present invention, when gas is converted into plasma and continuous processing is performed using the energy of the plasma, the plasma can be processed by a stable reaction. A reaction apparatus and a plasma reaction method can be realized.
【図１】本発明の実施の形態に係るガス分解装置の構成
図。Configuration diagram of a gas decomposition apparatus according to an embodiment of the present invention; FIG.
【図２】本発明の実施の形態に係るガス分解装置におけ
る気体の流れと平行なリアクターの断面図。2 is a cross-sectional view of the flow parallel to the reactor gas in the gas decomposition apparatus according to an embodiment of the present invention.
【図３】本発明の実施の形態に係るガス分解装置におけ
る気体の流れと垂直なリアクターの断面図。FIG. 3 is a cross-sectional view of the reactor perpendicular to the gas flow in the gas decomposition apparatus according to the embodiment of the present invention.
【図４】本発明の実施の形態に係るガス分解装置におけ
る接地電極板の断面図。FIG. 4 is a sectional view of a ground electrode plate in the gas decomposition device according to the embodiment of the present invention.
【図５】実施例１におけるリアクター温度と電流値の関
係を示すグラフ。FIG. 5 is a graph showing a relationship between a reactor temperature and a current value in Example 1.
【図６】比較例１におけるリアクター温度と電流値の関
係を示すグラフ。FIG. 6 is a graph showing a relationship between a reactor temperature and a current value in Comparative Example 1.
１：リアクター ２：交流電源 ３：変圧器 ４：温冷水器 ５：第１電極 ６：第２電極 ７：第３電極 ８：第４電極 ９：第５電極 １０：無機誘電体 １１：気体入口 １２：拡散空間 １３：絶縁体仕切り １４：気体出口 １５：側板 １６：配管 1: Reactor 2: AC power supply 3: Transformer 4: Hot / Water cooler 5: First electrode 6: Second electrode 7: Third electrode 8: Fourth electrode 9: Fifth electrode 10: Inorganic dielectric 11: Gas inlet 12: Diffusion space 13: Insulator partition 14: Gas outlet 15: Side plate 16: Piping
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田村 順一 東京都大田区下丸子３丁目30番２号 キヤ ノン株式会社内 Ｆターム(参考） 4G075 AA03 AA37 BA05 BD12 CA47 CA66 4H006 AA05 AC13 BA95 BC10 BC13 ────────────────────────────────────────────────── ─── front page of the continuation (72) inventor Junichi Tamura Ota-ku, Tokyo Shimomaruko 3-chome No. 30 No. 2 Canon Co., Ltd. in the F-term (reference) 4G075 AA03 AA37 BA05 BD12 CA47 CA66 4H006 AA05 AC13 BA95 BC10 BC13
Claims (20)
が配され、該電極間に気体が流れることが可能な構造を
有する無機誘電体が充填された構成を備え、該電極間に
放電を発生させて該電極間に存在する気体をプラズマ化
して処理するプラズマ反応装置であって、 前記リアクター内の温度を調節する温度調節手段を有す
ることを特徴とするプラズマ反応装置。A high-potential side electrode and a low-potential side electrode are provided in a reactor, and an inorganic dielectric having a structure through which gas can flow is filled between the electrodes. What is claimed is: 1. A plasma reactor for generating a discharge to convert a gas existing between said electrodes into plasma for processing, comprising a temperature control means for controlling a temperature in said reactor.
通させるための配管を配することによって構成されてい
ることを特徴とする請求項１に記載のプラズマ反応装
置。Wherein said temperature adjusting means, a plasma reactor according to claim 1, characterized in that it is constituted by arranging the piping for circulating the medium to the electrode.
地電極に前記配管が配されていることを特徴とする請求
項２に記載のプラズマ反応装置。Wherein the the electrode ground state of low potential side, the plasma reactor according to claim 2, characterized in that the pipe is arranged on the ground electrode.
いてプラズマ化することを特徴とする請求項１〜３のい
ずれか１項に記載のプラズマ反応装置。4. The plasma reactor according to claim 1, wherein a gas existing between the electrodes is turned into plasma under normal pressure.
とする請求項１〜４のいずれか１項に記載のプラズマ反
応装置。Wherein said discharge, plasma reactor according to any one of claims 1 to 4, characterized in that a glow discharge.
発性有機化合物を分解するように構成されていることを
特徴とする請求項１〜５のいずれか１項に記載のプラズ
マ反応装置。6. The plasma reactor according to claim 1, wherein the discharge is configured to decompose a volatile organic compound present in the gas.
能な隙間を有し、かつ該無機誘電体間の隙間で放電が発
生する構造を有することを特徴とする請求項１〜６のい
ずれか１項に記載のプラズマ反応装置。7. The method according to claim 1, wherein said inorganic dielectric has a gap through which gas can flow, and has a structure in which a discharge occurs in the gap between said inorganic dielectrics. the plasma reactor according to any one.
特徴とする請求項１〜７のいずれか１項に記載のプラズ
マ反応装置。Wherein said inorganic dielectric, the plasma reactor according to claim 1, which is a ferroelectric.
タン酸ストロンチウムから選択される少なくとも一つか
らなることを特徴とする請求項１〜８のいずれか１項に
記載のプラズマ反応装置。9. The plasma reactor according to claim 1, wherein the inorganic dielectric is made of at least one selected from barium titanate and strontium titanate.
特徴とする請求項１〜９のいずれか１項に記載のプラズ
マ反応装置。10. The plasma reactor according to claim 1, wherein the inorganic dielectric is a granular material.
極間に気体が流れることが可能な構造を有する無機誘電
体を充填し、該電極間に放電を発生させて該電極間に存
在する気体をプラズマ化して処理するプラズマ反応方法
であって、前記リアクター内を温度調節しながら、前記
気体をプラズマ化することを特徴とするプラズマ反応方
法。11. A reactor is filled with an inorganic dielectric having a structure through which gas can flow between electrodes on a high potential side and a low potential side, and a discharge is generated between the electrodes to cause a discharge between the electrodes. gas to a plasma reaction method for processing into plasma, while temperature control inside the reactor, a plasma reaction method, which comprises plasma of the gas.
極に配された配管を流通する媒体を介して行われること
を特徴とする請求項１１に記載のプラズマ反応方法。12. The plasma reaction method according to claim 11, wherein the temperature inside the reactor is adjusted via a medium flowing through a pipe arranged on the electrode.
接地電極に前記配管が配されていることを特徴とする請
求項１２に記載のプラズマ反応方法。Wherein said low-potential electrode and the ground state, a plasma reaction method according to claim 12, characterized in that the pipe in the ground electrode is disposed.
おいてプラズマ化することを特徴とする請求項１１〜１
３のいずれか１項に記載のプラズマ反応方法。14. The method according to claim 11, wherein the gas existing between the electrodes is turned into plasma under normal pressure.
4. The plasma reaction method according to any one of items 3.
徴とする請求項１１〜１４のいずれか１項に記載のプラ
ズマ反応方法。15. The plasma reaction method according to claim 11, wherein the discharge is a glow discharge.
揮発性有機化合物を分解することを特徴とする請求項１
１〜１５のいずれか１項に記載のプラズマ反応方法。16. The method according to claim 1, wherein the volatile organic compound present in the gas is decomposed by the discharge.
16. The plasma reaction method according to any one of 1 to 15.
可能な隙間を有し、かつ該無機誘電体間の隙間で放電が
発生する構造を有することを特徴とする請求項１１〜１
６のいずれか１項に記載のプラズマ反応方法。17. The structure according to claim 11, wherein said inorganic dielectric has a gap through which gas can flow, and has a structure in which a discharge is generated in the gap between said inorganic dielectrics.
7. The plasma reaction method according to any one of 6.
を特徴とする請求項１１〜１７のいずれか１項に記載の
プラズマ反応方法。18. The plasma reaction method according to claim 11, wherein said inorganic dielectric is a ferroelectric.
チタン酸ストロンチウムから選択される少なくとも一つ
からなることを特徴とする請求項１１〜１８のいずれか
１項に記載のプラズマ反応方法。19. The method according to claim 19, wherein the inorganic dielectric comprises barium titanate;
The plasma reaction method according to any one of claims 11 to 18, comprising at least one selected from strontium titanate.
特徴とする請求項１１〜１９のいずれか１項に記載のプ
ラズマ反応方法。20. The method of claim 19, wherein the inorganic dielectric, a plasma reaction method according to any one of claims 11 to 19 which is a granulate.
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| JP2001103738A JP2002292273A (en) | 2001-04-02 | 2001-04-02 | Plasma reactor and plasma reaction method |
| US10/112,750 US20020148562A1 (en) | 2001-04-02 | 2002-04-02 | Plasma reaction apparatus and plasma reaction method |
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| JP2001103738A JP2002292273A (en) | 2001-04-02 | 2001-04-02 | Plasma reactor and plasma reaction method |
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| US4970056A (en) * | 1989-01-18 | 1990-11-13 | Fusion Systems Corporation | Ozone generator with improved dielectric and method of manufacture |
| US5637198A (en) * | 1990-07-19 | 1997-06-10 | Thermo Power Corporation | Volatile organic compound and chlorinated volatile organic compound reduction methods and high efficiency apparatus |
| US5236672A (en) * | 1991-12-18 | 1993-08-17 | The United States Of America As Represented By The United States Environmental Protection Agency | Corona destruction of volatile organic compounds and toxics |
| US5534232A (en) * | 1994-08-11 | 1996-07-09 | Wisconsin Alumini Research Foundation | Apparatus for reactions in dense-medium plasmas |
| US6176078B1 (en) * | 1998-11-13 | 2001-01-23 | Engelhard Corporation | Plasma fuel processing for NOx control of lean burn engines |
| JP2000348896A (en) * | 1999-03-26 | 2000-12-15 | Canon Inc | Plasma generating method, plasma generating device, and gas treatment method in plasma reaction |
| SE516722C2 (en) * | 1999-04-28 | 2002-02-19 | Hana Barankova | Process and apparatus for plasma gas treatment |
| US6621227B1 (en) * | 2000-02-08 | 2003-09-16 | Canon Kabushiki Kaisha | Discharge generating apparatus and discharge generating method |
| KR100365368B1 (en) * | 2000-05-16 | 2002-12-18 | 한국기계연구원 | Method for treating toxic compounds using non-thermal plasma |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008201723A (en) * | 2007-02-20 | 2008-09-04 | Fuji Xerox Co Ltd | Microfluid device, reaction unit, and reaction method |
| JP7386238B2 (en) | 2018-10-02 | 2023-11-24 | オックスフォード インストルメンツ ナノテクノロジー ツールス リミテッド | electrode array |
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